All-solid battery including a solid electrolyte and a layer of polymer material

ABSTRACT

A process for producing all-solid, thin-layer batteries that do not lead to the appearance of phases at the interface between electrolyte layers to be assembled. Such a process for producing a battery may occur at low temperature without causing inter-diffusion phenomena at the interfaces with the electrodes.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a National Stage Application of PCTInternational Application No. PCT/FR2015/051819 (filed on Jul. 1, 2015),under 35 U.S.C. § 371, which claims priority to French PatentApplication No. 1456272 (filed on Jul. 1, 2014), which are each herebyincorporated by reference in their respective entireties.

TECHNICAL FIELD

This invention relates to the field of batteries and in particularlithium-ion batteries. It relates more specifically to all-solid lithiumion batteries (“Li-ion batteries”) and a novel process for producingsuch batteries.

BACKGROUND

Modes of producing lithium-ion batteries (“Li-ion batteries”) presentedin numerous articles and patents are known; the work “Advances inLithium-Ion Batteries” (ed. W. van Schalkwijk and B. Scrosati),published in 2002 (Kluever Academic/Plenum Publishers) provides a goodreview of the situation. The electrodes of Li-ion batteries may beproduced by means of printing or deposition techniques known to a personskilled in the art, and in particular by roll-coating, doctor blade ortape casting.

All-solid thin-layer Li-ion batteries having a planar architecture, i.e.which are essentially comprised of a set of three layers forming a basicbattery cell: an anode layer and a cathode layer separated by anelectrolyte layer are also known.

They use metallic lithium anodes and lithium phosphorus oxynitride filmsas the electrolyte. However, significant variations in volume of thelithium anode in charging and discharging steps makes it extremelydifficult to properly encapsulate the battery without the risk of lossof tightness of the encapsulation.

More recently, new all-solid battery architectures consisting of a stackof thin layers have been proposed. These batteries consist of a rigidand monobloc assembly of basic cells connected in parallel. Thesebatteries use dimensionally stable anodes to ensure the efficacy of theencapsulation, and enable three-dimensional structures to be produced,with better surface energy densities than the planar architectures. Suchbatteries are described in documents WO 2013/064779 A1 or WO 2012/064777A1. The batteries described in these documents do not contain organicsolvent-based liquid electrolyte, their structure consists of all-solidthin layers, without porosity in the electrode layers in order to ensuregood properties of stability of the battery over time. The process forproducing these batteries, also described in documents WO 2013/064779 A1or WO 2012/064777 A1, has numerous advantages because it makes itpossible to produce multilayer, thin-layer and therefore relativelynon-resistant assemblies, enabling performance in terms of power to bepreserved.

However, in some cases, the process of producing such batteries may havesome limits according to the materials used, in particular for theelectrolyte. In fact, ionic conductive glasses may be difficult toimplement. For example, solid electrolytes such as LiPON or lithiatedborates have a relatively low glass transition temperature, generallybetween around 250 and 300° C.: thus, during the step of assembly of thebattery by pressurized annealing of the different layers, theelectrolyte materials may partially crystallize, which may modify theirionic conduction property. Similarly, when the solid lithiumphosphorus-based electrolyte is used, it may be beneficial todifferentiate the chemical compositions of the electrolytes in contactwith the anodes and cathodes in order to optimize the performance of theelectrolytes.

However, the use of two lithium phosphorus-based electrolyteformulations deposited on each of the faces of the electrodes may leadto the appearance of new phases at the interface between the twoelectrolyte layers to be assembled, and may therefore modify theconduction properties.

Similarly, solid Li₇La₃Zr₂O₁₂ (called LLZO) electrolytes are good ionicconductors and are very stable in contact with anodes and cathodes, buttheir highly refractory character makes it sometimes difficult to weld,at low temperature, the electrodes to one another via the electrolytelayer without causing an interdiffusion phenomenon at the interfaceswith the electrodes.

SUMMARY

A first objective of the present invention is to propose a process forproducing all-solid thin-layer batteries that do not lead to theappearance of phases at the interface between the two electrolyte layersto be assembled.

Another objective of the present invention is to propose a process forproducing a battery at low temperature without causing interdiffusionphenomena at the interfaces with the electrodes.

Another objective of the invention is to produce thin-layer batteriescapable of being implemented by on an industrial level in a relativelysimple manner.

A first object of the invention concerns a process for producing anall-solid thin-layer battery including the following series of steps:

a) a layer including at least one anode material (referred to here as“anode material layer”) is deposited on its conductive substrate,preferably selected from the group formed by a metal sheet, a metalstrip, a metallized insulating sheet, a metallized insulating strip, ametallized insulating film, said conductive substrates, or conductiveelements thereof, capable of serving as an anode current collector;

b) a layer including at least one cathode material (referred to here as“cathode material layer”) is deposited on its conductive substrate,preferably selected from the group formed by a metal sheet, a metalstrip, a metallized insulating sheet, a metallized insulating strip, ametallized insulating film, said conductive substrates, or conductiveelements thereof, capable of serving as a cathode current collector,with the understanding that steps a) and b) can be reversed;

c) on at least one layer obtained in step a) and/or b), a layerincluding at least one solid electrolyte material (referred to here as“electrolyte material layer”) is deposited;

d) a layer of a cross-linked polymer material comprising ionic groupshaving a thickness of less than 10 μm, preferably less than 5 μm andeven more preferably less than 2 μm is deposited:

on the anode material layer coated with a solid electrolyte materiallayer and/or on the cathode material layer coated or not with a solidelectrolyte material layer;

or on the cathode material layer coated with a solid electrolytematerial layer and/or on the anode material layer coated or not with asolid electrolyte material layer;

e) an anode material layer obtained in step a), c) or d) is stacked faceto face in series with a cathode material layer obtained in step b), c)or d) with the understanding that the stack includes at least one solidelectrolyte material layer obtained in step c) and at least onecross-linked polymer material layer obtained in step d);

f) a heat treatment and/or a mechanical compression of the stackobtained in step e) is carried out in order to obtain an all-solidthin-layer battery.

The cross-linked polymer is preferably chosen from polymethylmethacrylates, polyamines, polyimides or polysiloxanes.

Preferably, the ionic groups of the polymer material are chosen from thefollowing cations: imidazolium, pyrazolium, tetrazolium, pyridinium,pyrrolidinium, such as n-propyl-n-methylpyrrolidinium (also calledPYR13) or n-butyl-n-methylpyrrolidinium (also called PYR14), ammonium,phosphonium or sulfonium; and/or from the following anions:bis(trifluoromethane)sulfonimide, bis(fluorosulfonyl)imide, orn-(nonafluorobutane-sulfonyl)-n-(trifluoromethanesulfonyl)-imide.

In a particular embodiment, the cross-linked polymer material isobtained by a step of polymerization of a mixture of monomers and/oroligomers and/or pre-polymers including one or more thermally orphotochemically polymerizable groups, said mixture of monomers and/oroligomers and/or pre-polymers including one or more reactive groupsenabling said ionic groups to be grafted.

Preferably, the thermal and/or photochemical polymerization is performeddirectly on the anode, cathode and/or electrolyte layer(s).

Advantageously, the deposition of the cross-linked polymer materialcomprising ionic groups is performed using at least one of the followingtechniques: dip-coating, spin-coating, roll coating, doctor blade,electrospraying or electrophoresis.

The thickness of the polymer material layer is less than 10 μm,preferably less than 5 μm and even more preferably less than 2 μm.Advantageously, the thickness of the polymer material layer is between0.5 and 1 μm.

The solid anode, cathode and electrolyte layers are deposited using atleast one of the following techniques: (i) physical vapor deposition(PVD), and more specifically by vacuum evaporation, laser ablation, ionbeam, or cathode sputtering; (ii) chemical vapor deposition (CVD), andmore specifically plasma-enhanced chemical vapor deposition (PECVD),laser-assisted chemical vapor deposition (LACVD), or aerosol-assistedchemical vapor deposition (AA-CVD); (iii) electrospraying; (iv)electrophoresis; (v) aerosol deposition; (vi) sol-gel; (vii) dipping,more specifically dip-coating, spin-coating or the Langmuir-Blodgettprocess.

Preferably, the anode, cathode and electrolyte layers are deposited byelectrospraying, electrophoresis, using an aerosol, or by dipping, andare preferably all deposited by electrophoresis.

In a particular embodiment, the layers of anode and/or cathode materialalso include electrically conductive materials, and in particulargraphite, and/or nanoparticles of lithium ion conductive materials, ofthe type used to produce electrolyte films, or cross-linked solidpolymer materials comprising ionic groups.

Preferably, the anode and/or cathode and/or electrolyte layers areproduced by a deposition of nanoparticles, respectively, of anode,cathode or electrolyte material using at least one of the followingtechniques: electrospraying, electrophoresis, aerosol deposition, anddipping. More specifically, the layers of anode, cathode and electrolytematerial nanoparticles are all deposited by electrophoresis.

According to the invention, the heat treatment is performed at atemperature of between 50° C. and 300° C., preferably between 100° C.and 200° C., and/or the mechanical compression of the layers to beassembled is performed at a pressure of between 10 and 100 MPa, andpreferably between 20 and 50 MPa.

The anode material layer a) is produced from a material chosen from:

(i) tin oxynitrides (typical formula SnOxNy);

(ii) lithiated iron phosphate (typical formula LiFePO₄);

(iii) mixed silicon and tin oxynitrides (typical formulaSi_(a)Sn_(b)O_(y)N_(z) with a>0, b>0, a+b≤2, 0<y≤4, 0<z≤3) (also calledSiTON), and in particular SiSn_(0.87)O_(1.2)N_(1.72); as well asoxynitrides with the typical form Si_(a)Sn_(b)C_(c)O_(y)N_(z) with a>0,b>0, a+b≤2, 0<c<10, 0<y<24, 0<z<17; Si_(a)Sn_(b)C_(c)O_(y)N_(z)X_(n)with X_(n) comprising at least one of the elements among F, Cl, Br, I,S, Se, Te, P, As, Sb, Bi, Ge, Pb and a>0, b>0, a+b>0, a+b≤2, 0<c<10,0<y<24 and 0<z<17; and Si_(a)Sn_(b)O_(y)N_(z)X_(n) with X_(n) comprisingat least one of the elements among F, Cl, Br, I, S, Se, Te, P, As, Sb,Bi, Ge, Pb and a>0, b>0, a+b≤2, 0<y≤4 and 0<z≤3;

(iv) nitrides of type Si_(x)N_(y) (in particular with x=3 and y=4),Sn_(x)N_(y) (in particular with x=3 and y=4), Zn_(x)N_(y) (in particularwith x=3 and y=4), Li_(3-x)M_(x)N (with M=Co, Ni, Cu);

(v) the oxides SnO₂, Li₄Ti₅O₁₂, SnB_(0.6)P_(0.4)O_(2.9), and TiO₂.

The cathode material layer b) is produced from cathode material chosenfrom:

(i) the oxides LiMn₂O₄, LiCoO₂, LiNiO₂, LiMn_(1.5)Ni_(0.5)O₄,LiMn_(1.5)Ni_(0.5−x)X_(x)O₄ (in which X is selected from Al, Fe, Cr, Co,Rh, Nd, other rare earth elements, and in which 0<x<0.1), LiFeO₂, andLiMn_(1/3)Ni_(1/3)Co_(1/3)O₄;

(ii) the phosphates LiFePO₄, LiMnPO₄, LiCoPO₄, LiNiPO₄, Li₃V₂(PO₄)₃; andthe phosphates of formula LiMM′PO₄, with M and M′ (M≠M′) selected fromFe, Mn, Ni, Co, V;

(iii) all lithiated forms of the following chalcogenides: V₂O₅, V₃O₈,TiS₂, titanium oxysulfides (TiO_(y)S_(z)), tungsten oxysulfides(WO_(y)S_(z)), CuS, and CuS₂.

The electrolyte material layer c) is produced from electrolyte materialchosen from:

garnets of formula:Li_(d)A_(1x)A_(2y)(TO₄)_(z), wherein:

-   -   A1 represents a cation of oxidation number +II, preferably Ca,        Mg, Sr, Ba, Fe, Mn, Zn, Y, Gd; and wherein    -   A2 represents a cation of oxidation number +III, preferably Al,        Fe, Cr, Ga, Ti, La; and wherein    -   (TO₄) represents an anion in which T is an atom of oxidation        number +IV, located at the center of a tetrahedron formed by        oxygen atoms, and in which TO₄ advantageously represents the        silicate or zirconate anion, with the understanding that all or        some of the elements T with an oxidation number +IV may be        replaced by atoms with an oxidation number +III or +V, such as        Al, Fe, As, V, Nb, In, Ta;    -   with the understanding that: d is between 2 and 10, preferably        between 3 and 9, and even more preferably between 4 and 8; x is        3 but may be between 2.6 and 3.4 (preferably between 2.8 and        3.2); y is 2 but may be between 1.7 and 2.3 (preferably between        1.9 and 2.1); and z is 3 but may be between 2.9 and 3.1;

the garnets, preferably chosen from: Li₇La₃Zr₂O₁₂, Li₆La₂BaTa₂O₁₂;Li_(5.5)La₃Nb_(1.75)In_(0.25)O₁₂; Li₅La₃M₂O₁₂, with M=Nb or Ta or amixture of the two compounds; Li_(7−x)Ba_(x)La_(3−x)M₂O₁₂ with 0≤x≤1 andM=Nb or Ta or a mixture of the two compounds;Li_(7−x)La₃Zr_(2−x)M_(x)O₁₂ with 0≤x≤2 and M=Al, Ga or Ta or a mixtureof two or three of said compounds;

lithiated phosphates, preferably chosen from: Li3PO4; Li₃PO₄;Li₃(Sc_(2−x)M_(x))(PO₄)₃ with M=Al or Y and 0≤x≤1;Li_(1+x)M_(x)(Sc)_(2−x)(PO₄)₃ with M=Al, Y, Ga or a mixture of the threecompounds and 0≤x≤0.8; Li_(1+x)M_(x)(Ga_(1−y)Sc_(y))_(2−x)(PO₄)₃ with0≤x≤0.8; 0≤y≤1 and M=Al or Y or a mixture of the two compounds;Li_(1+x)M_(x)(Ga)_(2−x)(PO₄)₃ with M=Al, Y or a mixture of the twocompounds and 0≤x≤0.8; Li_(1+x)Al_(x)Ti_(2−x)(PO₄)₃ with 0≤x≤1, orLi_(1+x)Al_(x)Ge_(2−x)(PO₄)₃ with 0≤x≤1; orLi_(1+x+z)M_(x)(Ge_(1−y)Ti_(y))_(2−x)Si_(z)P_(3−z)O₁₂ with 0≤x≤0.8 and0≤y≤1.0 and 0≤z≤0.6 and M=Al, Ga or Y or a mixture of two or three ofsaid compounds; Li_(3+y)(Sc_(2−x)M_(x))Q_(y)P_(3−y)O₁₂ with M=Al and/orY and Q=Si and/or Se, 0≤x≤0.8 and 0≤y≤1; orLi_(1+x+y)M_(x)Sc_(2−x)Q_(y)P_(3−y)O₁₂ with M=Al, Y, Ga or a mixture ofthe three compounds and Q=Si and/or Se, 0≤x≤0.8 and 0≤y≤1; orLi_(1+x+y+z)M_(x)(Ga_(1−y)Sc_(y))_(2−x)Q_(z)P_(3−z)O₁₂ with 0≤x≤0.8;0≤y≤1; 0≤z≤0.6 with M=Al or Y or a mixture of the two compounds and Q=Siand/or Se; or Li_(1+x)N_(x)M_(2−x)P₃O₁₂ with 0≤x≤1 and N═Cr and/or V,M=Se, Sn, Zr, Hf, Se or Si, or a mixture of these compounds;

lithiated borates, preferably chosen from: Li₃(Sc_(2−x)M_(x))(BO₃)₃ withM=Al or Y and 0≤x≤1; Li_(1+x)M_(x)(Sc)_(2−x)(BO₃)₃ with M=Al, Y, Ga or amixture of the three compounds and 0≤x≤0.8; 0≤y≤1;Li_(1+x)M_(x)(Ga_(1−y)Sc_(y))_(2−X)(BO₃)₃ with 0≤x≤0.8; 0≤y≤1 and M=Alor Y; Li_(1+x)M_(x)(Ga)_(2−x)(BO₃)₃ with M=Al, Y or a mixture of the twocompounds and 0≤x≤0.8; 0≤y≤1; Li₃BO₃, Li₃BO₃—Li₂SO₄, Li₃BO₃—Li₂SiO₄,Li₃BO₃—Li₂SiO₄—Li2SO₄;

oxynitrides, preferably chosen from Li₃PO_(4−x)N_(2x/3),Li₄SiO_(4−x)N_(2x/3), Li₄GeO_(4−x)N_(2x/3) with 0<x<4 orLi₃BO_(3−x)N_(2x/3) with 0<x<3; the materials based on lithium,phosphorus or boron oxynitrides (called LiPON and LIBON) may alsocontain silicon, sulfur, zirconium, aluminum, or a combination ofaluminum, boron, sulfur and/or silicon, and boron for lithiumphosphorus;

lithiated oxides, preferably chosen from Li₇La₃Zr₂O₁₂ orLi_(5+x)La₃(Zr_(X),A_(2−x))O₁₂ with A=Sc, Y, Al, Ga and 1.4≤x≤2 orLi_(0.35)La_(0.55)TiO₃;

silicates, preferably chosen from Li₂SiO₅, Li₂SiO₃, Li₂Si₂O₆, LiAlSiO₄,Li₄SiO₄, LiAlSi₂O₆.

The electrolyte material layer c) stable in contact with the anodesfunctioning at significantly reducing potentials is produced fromelectrolyte material chosen from:

garnets of formula:Li_(d)A1_(x)A_(2y)(TO₄)_(z) wherein:

-   -   A1 represents a cation of oxidation number +II, preferably Ca,        Mg, Sr, Ba, Fe, Mn, Zn, Y, Gd; and wherein    -   A2 represents a cation of oxidation number +III, preferably Al,        Fe, Cr, Ga, Ti, La; and wherein    -   (TO₄) represents an anion in which T is an atom of oxidation        number +IV, located at the center of a tetrahedron formed by        oxygen atoms, and in which TO₄ advantageously represents the        silicate or zirconate anion, with the understanding that all or        some of the elements T with an oxidation number +IV may be        replaced by atoms with an oxidation number +III or +V, such as        Al, Fe, As, V, Nb, In, Ta;    -   with the understanding that: d is between 2 and 10, preferably        between 3 and 9, and even more preferably between 4 and 8; x is        3 but may be between 2.6 and 3.4 (preferably between 2.8 and        3.2); y is 2 but may be between 1.7 and 2.3 (preferably between        1.9 and 2.1); and z is 3 but may be between 2.9 and 3.1;

the garnets, preferably chosen from: Li₇La₃Zr₂O₁₂; Li₆La₂BaTa₂O₁₂;Li_(5.5)La₃Nb_(1.75)In_(0.25)O₁₂; Li₅La₃M₂O₁₂ with M=Nb or Ta or amixture of the two compounds; Li_(7−x)Ba_(x)La_(3−x)M₂O₁₂ with 0≤x≤1 andM=Nb or Ta or a mixture of the two compounds;Li_(7−x)La₃Zr_(2−x)M_(x)O₁₂ with 0≤x≤2 and M=Al, Ga or Ta or a mixtureof two or three of said compounds;

lithiated phosphates, preferably chosen from: Li₃PO₄;Li₃(Sc_(2−x)M_(x))(PO₄)₃ with M=Al or Y and 0≤x≤1;Li_(1+x)M_(x)(Sc)_(2−x)(PO₄)₃ with M=Al, Y, Ga or a mixture of the threecompounds and 0≤x≤0.8; Li_(1+x)M_(x)(Ga_(1−y)Sc_(y))_(2−x)(P_(O4))₃ with0≤x≤0.8; 0≤y≤1 and M=Al or Y or a mixture of the two compounds;Li_(1+x)M_(x)(Ga)_(2−x)(PO₄)₃ with M=Al, Y or a mixture of the twocompounds and 0≤x≤0.8; Li_(+x)Al_(x)Ti_(2−x)(PO₄)₃ with 0≤x≤1 orLi_(1+x)Al_(x)Ge_(2−x)(PO₄)₃ with 0≤x≤1; orLi_(1+x+y)M_(x)Ge_(1−y)Ti_(y))_(2−x)Si_(z)P_(3-z)O₁₂ with 0≤x≤0.8 and0≤y≤1.0 and 0≤z≤0.6 and M=Al, Ga or Y or a mixture of two or three ofsaid compounds; Li_(3+y)(Sc_(2−x)M_(x))Q_(y)P_(3−y)O₁₂, with M=Al and/orY and Q=Si and/or Se, 0≤x≤0.8 and 0≤y≤1; orLi_(1+x+y)M_(x)Sc_(2−x)Q_(y)P_(3−y)O₁₂, with M=Al, Y, Ga or a mixture ofthe three compounds and Q=Si and/or Se, 0≤x≤0.8 and 0≤y≤1; orLi_(1+x+y+z)M_(x)(Ga_(1−y)Sc_(y))_(2−x)Q_(z)P_(3-z)O₁₂ with 0≤x≤0.8;0≤y≤1; 0≤z≤0.6 with M=Al or Y or a mixture of the two compounds and Q=Siand/or Se; or Li_(1+x)N_(x)M_(2−x)P₃O₁₂, with 0≤x≤1 and N═Cr and/or V,M=Se, Sn, Zr, Hf, Se or Si, or a mixture of these compounds;

lithiated borates, preferably chosen from: Li₃(Sc_(2−x)M_(x))(BO₃)₃ withM=Al or Y and 0≤x≤1; Li_(1+x)M_(x)(Sc)_(2−x)(BO₃)₃ with M=Al, Y, Ga or amixture of the three compounds and 0≤x≤0.8; 0≤y≤1;Li_(1+x)M_(x)(Ga_(1−y)Sc_(y))_(2−X)(BO₃)₃ with 0≤x≤0.8; 0≤y≤1 and M=Alor Y; Li_(1+x)M_(x)(Ga)_(2−x)(BO₃)₃ with M=Al, Y or a mixture of the twocompounds and 0≤x≤0.8; 0≤y≤1; Li₃BO₃, Li₃BO₃—Li₂SO₄, Li₃BO₃—Li₂SiO₄,Li₃BO₃—Li₂SiO₄—Li₂SO₄;

oxynitrides, preferably chosen from Li₃PO_(4−x)N_(2x/3),Li₄SiO_(4−x)N_(2x/3), Li₄GeO_(4−x)N_(2x/3) with 0<x<4 orLi₃BO_(3−x)N_(2x/3) with 0<x<3; the materials based on lithium,phosphorus or boron oxynitrides (called LiPON and LIBON) may alsocontain silicon, sulfur, zirconium, aluminum, or a combination ofaluminum, boron, sulfur and/or silicon, and boron for lithiumphosphorus;

lithiated oxides, preferably chosen from Li₇La₃Zr₂O₁₂ orLi_(5+x)La₃(Zr_(X),A_(2−x))O₁₂ with A=Sc, Y, Al, Ga and 1.4≤x≤2 orLi_(0.35)La_(0.55)TiO₃;

silicates, preferably chosen from Li₂Si₂O₅, Li₂SiO₃, Li₂Si₂O₆, LiAlSiO₄,Li₄SiO₄, LiAlSi₂O₆.

These electrolytes may be used with all of the anode chemicalcompositions.

By adding a layer of a cross-linked polymer material comprising ionicgroups, to the anode (respectively cathode) material layer coated with asolid electrolyte material layer and/or to the cathode (respectivelyanode) material layer coated or not with a solid electrolyte materiallayer, it is possible to associate said electrolyte material layer c),which is stable in contact with the anodes, with other solid electrolyteformulations that would be exclusively in contact with the cathodes.These electrolytes stable only in contact with the cathodes areperovskites of formulas Li_(3x)La_(2/3−x□1/3−x)TiO₃,La_(2/3−x)Sr_(x□1/3−x)Li_(x)TiO₃ andLa_(2/3)Li_(x□1/3−x)Ti_(1−x)Al_(x)O₃ wherein □ represents a vacancypresent in the structure. Thus, for Li_(3x)La_(2/3−x□1/3−x)TiO₃, thecomposition includes a lanthanum vacancy in said composition capable ofvarying between 2/3-x and 1/3-x, with 0<x<0.20 and preferably 0<x<0.16;for La_(2/3−x)Sr_(x□1/3−x)Li_(x)TiO₃, the composition includes astrontium vacancy, the proportion of strontium in said composition beingcapable of varying between x and 1/3-x, with 0<x<0.20 and preferably0<x<0.16; and for La_(2/3)Li_(x□1/3−x)Ti_(1−x)Al_(x)O₃, the compositionincludes a lithium vacancy, the proportion of lithium in saidcomposition being capable of varying between x and 1/3-x, with 0<x<0.20and preferably 0<x<0.16. In a particular embodiment, the process alsoincludes a step g) of encapsulation of the battery obtained in step f)by deposition of at least one ceramic, vitreous or vitroceramic materialencapsulation layer;

Advantageously, anode and cathode terminals are produced bymetallization of the sections cut, preferably by deposition of a tinlayer, optionally deposited on a sub-layer of nickel and/or epoxy resinfilled with metal particles.

Preferably, the size of the nanoparticles of electrolyte material issmaller than 100 nm, and preferably smaller than 30 nm.

The conductive substrates are made of aluminum, copper, stainless steel,titanium or nickel, preferably nickel, and optionally coated with anoble metal chosen from the following metals: gold, platinum, palladium,vanadium, cobalt, nickel, manganese, niobium, tantalum, chromium,molybdenum, titanium, palladium, zirconium, tungsten or any alloycontaining at least one of these metals.

Another object of the invention concerns a battery capable of beingobtained by the process according to the invention.

Advantageously, the surface capacity of the cathode is greater than orequal to the surface capacity of the anode.

In a preferred embodiment, the stack of cathode and anode layers islaterally offset.

Advantageously, the battery includes at least one encapsulation layer,preferably a ceramic, glass or vitroceramic layer. Even moreadvantageously, the battery includes a second encapsulation layerdeposited on said first encapsulation layer, said second encapsulationlayer preferably being silicone.

Preferably, said at least one encapsulation layer entirely covers fourof the six faces of said battery and partially covers the two remainingfaces, located below the metallizations intended for the connections ofthe battery.

In a particular embodiment, the battery includes terminals where thecathode and anode current collectors, respectively, are exposed.

Advantageously, the anode connections and the cathode connections arelocated on opposite sides of the stack.

DRAWINGS

FIGS. 1 and 2 shows the charge and discharge curves obtained for anall-solid battery.

DESCRIPTION

In the context of the present invention, “electrophoretic deposition” or“deposition by electrophoresis” refers to a layer deposited by a processof depositing particles previously suspended in a liquid medium, onto apreferably conductive substrate, the displacement of the particles tothe surface of the substrate being generated by application of anelectric field between two electrodes placed in the suspension, one ofthe electrodes constituting the conductive substrate on which thedeposition is performed, and the other electrode (“counter electrode”)being placed in the liquid phase. A so-called “dense” deposition ofparticles forms on the substrate, if the zeta potential of the particlesuspension has an appropriate value, and/or after a specific thermaland/or mechanical densification treatment. This deposition has aparticular structure recognizable to a person skilled in the art, whocan distinguish it from depositions obtained by any other technique.

In the context of the present document, the size of a particle is itslargest dimension. Thus, a “nanoparticle” is a particle of which atleast one of the dimensions is less than 100 nm. The “particle size” or“mean particle size” of a powder or a group of particles is given asD50.

An “all-solid” battery is a battery not containing liquid phasematerial.

The “surface capacity” of an electrode refers to the quantity of lithiumion capable of being inserted into an electrode (expressed as mA·h/cm2).

In the context of the present invention, garnet-type compounds may beused, in particular as the electrolyte, in which the ionic conductivityis ensure by lithium ions. The chemical composition of garnets isvariable according to the isomorphic substitution of the different atomsconstituting its basic formula Li_(d)A1_(x)A2_(y)(TO₄)_(z). In thisformula, Li represents a lithium cation. The value d is between 2 and10, preferably between 3 and 9, and even more preferably between 4 and8. In this formula A1 represents a cation of oxidation number +II, atthe pseudocubic coordination site 8. The value x is typically 3, but itmay have a stoichiometric deviation. A1 may for example be C, Mg, Sr,Ba, Fe, Mn, Zn, Y, Gd. A2 represents a cation of oxidation number +III,at the octahedral coordination site 6. The value y is typically 2, butthere may be a stoichiometric deviation. A2 may for example be Al, Fe,Cr, Ga, Ti, La. A1 and A2 may represent the same cation. TO₄ representsan anion in which the four oxygen atoms form a tetrahedron, the cation Tbeing at the center of the tetrahedron; T represents primarily a cationof oxidation number +IV, and primarily silicon. In this last case, TO₄represents the silicate anion (SiO₄)⁴⁻ and these garnets are thenconsidered to be nesosilicates, the structure of which may be describedby a three-dimensional network formed by (SiO₄) tetrahedra connected bythe apex to octahedra A2O₆. The cavities formed have a distorted cubeshape A1O₈ (dodecahedra). Each tetrahedron shares its apexes with fourdifferent octahedral. Each octahedral is bound at the apex to sixdifferent tetrahedral and at the edge to six dodecahedra. Eachdodecahedra shares its edges with four other dodecahedra, fouroctahedral and two tetrahedral. Only two of its edges are not shared. Tmay also be the cation Zr₄₊. All or some of the elements T with anoxidation number +IV may be replaced by atoms with an oxidation number+III or +V, such as: Al, Fe, As, V, Nb, In, Ta, Zr; this may cause anadjustment in the molar amount of oxygen in the formulaLi_(d)A1_(x)A2_(y)(TO₄)_(z). In this formula, the atoms A1, A2, T, and Omay be subject to isomorphic substitution. This isomorphic substitutionmay be of different types, and primarily two types: the same number ofatoms may be replaced by the same number of different atoms of the samevalence (so-called first-species isomorphisms), an atom may be replacedby another atom with a similar ionic radius and a valence that differsby one unit (so-called second-species isomorphism, by so-calledaliovalent substitution); in this second case, the electrical neutralityis ensured either by a corresponding replacement in the crystallographicnetwork, or by a vacancy, or by a mobile interstitial ion (anion orcation); this mobile interstitial ion may be lithium. In the formulaindicated above, the number z is normally equal to 3 or close to 3. Asmall part of the oxygen atoms may optionally be bound to a hydrogenatom (OH group rather than O). A small portion of the groups (TO₄) mayalso be replaced by OH groups; in this case, it (TO₄)_(3−p)(OH)_(4p)should be written instead of (TO₄)₃. The oxygen may be replaced at leastpartially by bivalent or trivalent anions (such as N³⁻);

Garnet-based ionic conductors with mobile lithium ions are described,for example, in documents WO 2005/085138, WO 2009/003695 and WO2010/090301. The lithium ions occupy crystallographic sites and may alsobe in the interstitial position.

In the context of the present invention, the garnet-type compounds are,preferably, chosen from:

Li₇La₃Zr₂O₁₂;

Li₆La₃BaTa₂O₁₂;

Li_(5.5)La₃Nb_(1.75)In_(0.25)O₁₂;

Li₅La₃M₂O₁₂ with M=Nb or Ta or a mixture of the two compounds;

Li_(7−x)Ba_(x)La_(3−x)M₂O₁₂ with 0≤x≤1 and M=Nb or Ta or a mixture ofthe two compounds; and

Li_(7−x)La_(x)Zr_(2−x)M_(x)O₁₂ with 0≤x≤2 and M=Al, Ga or Ta or amixture of two or three of said compounds;

To respond to the above-mentioned disadvantages, the inventor hasdeveloped a new process for producing an all-solid battery, notcontaining organic solvents so that they can be heated without the riskof combustion. The objectives are achieved by the implementation of aprocess for producing a thin-layer battery including at least one layerof a cross-linked polymer material comprising ionic groups. Thebatteries obtained by the process according to the invention have amultilayer structure, by contrast with planar structures of theconventional thin-layer batteries, in order to obtain batteries havinggood energy and power density. In addition, the process for obtainingthese batteries makes it possible to produce an assembly of batterylayers at a relatively low temperature, i.e. at a temperature below 300°C., without reducing the surface capacities of the electrodesconstituting the resulting battery. The production of an “all-solid”battery requires the use of dimensionally stable materials, in order tomake the behavior of the battery reliable, in particular with regard tolimiting deformation constraints on the encapsulation or on theelectrodes.

The solid anode, cathode and electrolyte layers are deposited using oneof the following techniques: i) physical vapor deposition (PVD), andmore specifically vacuum evaporation, laser ablation, ion beam, cathodesputtering; ii) chemical vapor deposition (CVD), and more specificallyplasma-enhanced chemical vapor deposition (PECVD), laser-assistedchemical vapor deposition (LACVD), or aerosol-assisted chemical vapordeposition (AA-CVD); iii) electrospraying; iv) electrophoresis; v)aerosol deposition; vi) sol-gel; vii) dipping, more specificallydip-coating, spin-coating or the Langmuir-Blodgett process.

According to the invention, the solid anode, cathode and electrolytelayers are advantageously deposited by electrophoresis. Theelectrophoretic deposition of particles is performed by applying anelectric field between the substrate on which the deposition is producedand a counter electrode, enabling the charged particles of the colloidalsuspension to move and be deposited on the substrate. The absence ofbinders and other solvents deposited at the surface with the particlesmakes it possible to obtain very compact depositions. The compactnessobtained owing to the electrophoretic deposition limits and evenprevents the risks of cracks or the appearance of other defects in thedeposition during the drying steps. In addition, the deposition rate maybe high owing to the electric field applied and the electrophoreticmobility of the particles of the suspension.

According to the invention, the process for producing an all-solidbattery includes a step a) of deposition of an anode material layer. Thematerials chosen for the anode material layer are preferably chosen fromthe following materials:

i) tin oxynitrides (typical formula SnO_(x)N_(y));

ii) lithiated iron phosphate (typical formula LiFePO₄);

iii) mixed silicon and tin oxynitrides (typical formulaSi_(a)Sn_(b)O_(y)N_(z) with a>0, b>0, a+b≤2, 0<y≤4, 0<z≤3) (also calledSiTON), and in particular SiSn_(0.87)O_(1.2)N_(1.72); as well asoxynitrides in the form Si_(a)Sn_(b)C_(c)O_(y)N_(z) with a>0, b>0,a+b≤2, 0<c−10, 0<y<24, 0<z<17; Si_(a)Sn_(b)C_(c)O_(y)N_(z)X_(n) withX_(n) at least one of the elements among F, Cl, Br, I, S, Se, Te, P, As,Sb, Bi, Ge, Pb and a>0, b>0, a+b>0, a+b≤2, 0<c<10, 0<y<24 and 0<z<17;and Si_(a)Sn_(b)O_(y)N_(z)X_(n) with X_(n) at least one of the elementsamong F, Cl, Br, I, S, Se, Te, P, As, Sb, Bi, Ge, DPb and a>0, b>0,a+b≤2, 0<y≤4 and 0<z≤3;

iv) nitrides of type Si_(x)N_(y) (in particular with x=3 and y=4),Sn_(x)N_(y) (in particular with x=3 and y=4), Zn_(x)N_(y) (in particularwith x=3 and y=4), Li_(3−x)M_(x)N (with M=Co, Ni, Cu); and

v) the oxides SnO₂, Li₄Ti₅O₁₂, SnB_(0.6)P_(0.4)O_(2.9) and TiO₂.

Li₄T₅O₁₂ for producing the anode layer is particularly preferred. Inaddition, Li₄T₅O₁₂ is a lithium insertion material reversibly insertinglithium ions without causing deformation of the host material.

According to the invention, the process for producing an all-solidbattery includes a step b) of depositing a cathode material layer. Thecathode material layer is preferably produced by electrophoresis. Thematerials chosen for the cathode material layer are preferably chosenfrom the following materials:

i) the oxides LiMn₂O₄, LiCoO₂, LiNiO₂, LiMn_(1.5)Ni_(0.5)O₄,LiMn_(1.5)Ni_(0.5−x)X_(x)O₄ (in which X is selected from Al, Fe, Cr, Co,Rh, Nd, other rare earth elements, and in which 0<x<0.1), LiFeO₂,LiMn_(1/3)Ni_(1/3)Co_(1/3)O₄;

ii) the phosphates LiFePO₄, LiMnPO₄, LiCoPO₄, LiNiPO₄, Li₃V₂(PO₄)₃;

iii) all lithiated forms of the following chalcogenides: V₂O₅, V₃O₈,TiS₂, titanium oxysulfides (TiO_(y)S_(z)), tungsten oxysulfides(WO_(y)S_(z)), CuS, CuS₂;

The cathode electrode, consisting of a thin layer of LiMn₂O₄ depositedon a metal substrate, preferably nickel, is advantageously producedwithout using vacuum techniques or dry rooms—equipment that is veryexpensive to implement. In fact, LiMn₂O₄ like LiMn_(1.5)Ni_(0.5)O₄, isnot spontaneously sensitive to air. It is, however, recommended to avoidprolonged exposure. The impact of the exposures of cathode materials toair during production of the electrodes remains negligible with regardto the relatively short implementation times.

To produce the anode or cathode, it is possible to add to theabove-cited nanoparticles of electrically conductive materials, and inparticular graphite, and/or nanoparticles of ionic conductive materials,of the type used to produce electrolyte films (described below), orcross-linked polymer materials comprising ionic groups.

Advantageously, the depositions of the anode and cathode material layerare performed by an electrophoretic deposition of anode and cathodematerial nanoparticles, respectively.

Advantageously, the depositions of the layer of anode and cathodematerial nanoparticles are performed directly on the metal substrate.For small nanoparticle sizes, i.e. less than 100 nm, the deposition ofanode, cathode and electrolyte layers are performed by electrospraying,electrophoresis, aerosol deposition, or dipping. Advantageously, theanode, cathode and electrolyte layers are all deposited byelectrophoresis. This particular embodiment of the process according tothe invention makes it possible to obtain a dense and compact layer ofnanoparticles, in particular by self-sintering of the nanoparticle layerduring the step of electrophoretic deposition, drying and/or heattreatment at low temperature. In addition, as the electrophoreticdeposition of the layer of anode or cathode material nanoparticles iscompact, the risk of cracking of the layer after drying is reduced,unlike the nanoparticle layers produced from inks or fluids, having lowdry extract contents and for which the deposits contain large quantitiesof solvent, which, after drying leads to the appearance of cracks in thedeposit, which is detrimental to the operation of a battery.

According to the invention, the deposition of the layer of anode orcathode material nanoparticles is performed directly on its conductivesubstrate, preferably a metal conductive substrate chosen from thefollowing materials: nickel, aluminum, stainless steel, titanium orcopper. In a preferred embodiment, the deposition of the layer of anodeor cathode material nanoparticles is performed on a nickel substrate.The thickness of the substrate is less than 10 μm, and preferably lessthan 5 μm.

The conductive substrates may be used in the form of sheets, optionallysheets including pre-cut electrode patterns or in the form of strips. Toimprove the quality of the electrical contacts with the electrodes, thesubstrates may advantageously be coated with a metal or a metal alloy,preferably chosen from gold, chromium, stainless steel, palladium,molybdenum, titanium, tantalum or silver.

According to the invention, the deposition of a layer of anode orcathode material nanoparticles directly onto its conductive substrate,for example, by electrophoresis, makes it possible to obtain a densenanocrystalline structure layer. However, the formation of grainboundaries is possible, leading to the formation of a layer having aparticular structure, between that of an amorphous and crystallizedmaterial, which may in certain cases limit the kinetics of diffusion ofthe lithium ions in the thickness of the electrode. Thus, the power ofthe battery electrode and the life cycle may be affected.Advantageously, to improve the performance of the battery, arecrystallization heat treatment is performed in order to improve thecrystallinity, and the electrode is optionally consolidated in order toreinforce the power of the electrodes (anode and/or cathode).

The recrystallization heat treatment of the anode and/or cathode layeris performed at a temperature of between 300° C. and 1000° C.,preferably between 400° C. and 800° C., and even more preferably between500° C. and 700° C. The heat treatment must be performed after step a)and/or b) of deposition of the anode and/or cathode layer, but beforestep c) of deposition of the electrolyte layer.

According to the invention, the process for producing a battery includesa step c) of deposition of an electrolyte material layer. The depositionof the electrolyte material layer is performed on the anode materiallayer and/or on the cathode material layer.

The deposition of a solid electrolyte layer on the anode and/or cathodelayer makes it possible to protect the electrochemical cell from aninternal short-circuit. It also makes it possible to produce anall-solid battery with a long lifetime, and which is easy to produce.The deposition of the electrolyte material layer is preferably performedby electrophoresis.

More specifically, the materials chosen as electrolyte materials arepreferably chosen from the following materials:

on a layer obtained at stage a) and/or b):

-   -   garnets of formula:        Li_(d)A1_(x)A2_(y)(TO₄)_(z) wherein:        -   A1 represents a cation of oxidation number +II, preferably            Ca, Mg, Sr, Ba, Fe, Mn, Zn, Y, Gd; and wherein        -   A2 represents a cation of oxidation number +III, preferably            Al, Fe, Cr, Ga, Ti, La; and wherein        -   (TO₄) represents an anion in which T is an atom of oxidation            number +IV, located at the center of a tetrahedron formed by            oxygen atoms, and in which TO₄ advantageously represents the            silicate or zirconate anion, with the understanding that all            or some of the elements T with an oxidation number +IV may            be replaced by atoms with an oxidation number +III or +V,            such as Al, Fe, As, V, Nb, In, Ta;        -   with the understanding that: d is between 2 and 10,            preferably between 3 and 9, and even more preferably between            4 and 8; x is 3 but may be between 2.6 and 3.4 (preferably            between 2.8 and 3.2); y is 2 but may be between 1.7 and 2.3            (preferably between 1.9 and 2.1); and z is 3 but may be            between 2.9 and 3.1;    -   the garnets, preferably chosen from: Li₇La₃Zr₂O₁₂;        Li₆La₂BaTa₂O₁₂; Li_(5.5)La₃Nb_(1.75)In_(0.25)O₁₂; Li₅La₃M₂O₁₂        with M=Nb or Ta or a mixture of the two compounds;        Li_(7−x)Ba_(x)La_(3−x)M₂O₁₂ with 0≤x≤1 and M=Nb or Ta or a        mixture of the two compounds; Li_(7−x)La₃Zr_(2−x)M_(x)O₁₂ with        0≤x≤2 and M=Al, Ga or Ta or a mixture of two or three of said        compounds;    -   lithiated phosphates, preferably chosen from: Li₃PO₄;        Li₃(Sc_(2−x)M_(x))(PO₄)₃ with M=Al or Y and 0≤x≤1;        Li_(1+x)M_(x)(Sc)_(2−x)(PO₄)₃ with M=Al, Y, Ga or a mixture of        the three compounds and 0≤x≤0.8;        Li_(1+x)M_(x)(Ga_(1−y)Sc_(y))_(2−x)(PO₄)₃ with 0≤x≤0.8; 0≤y≤1        and M=Al or Y or a mixture of the two compounds; Li        Li_(1+x)M_(x)(Ga)_(2−x)(PO₄)₃ with M=Al, Y or a mixture of the        two compounds and 0≤x≤0.8; Li_(1+x)Al_(x)Ti_(2−x)(PO₄)₃ with        0≤x≤1, or Li_(1+x)Al_(x)Ge_(2−x)PO₄)₃ with 0≤x≤1; or        Li_(1+x+z)M_(x)(Ge_(1−y)Ti_(y))_(2−x)Si_(z)P_(3−z)O₁₂ with        0≤x≤0.8 and 1≤y≤1.0 and 0≤z≤0.6 and M=Al, Ga or Y or a mixture        of two or three of said compounds;        Li_(3+y)(Sc_(2−x)M_(x))Q_(y)P_(3-y)O₁₂, with M=Al and/or Y and        Q=Si and/or Se, 0≤x≤0.8 and 0≤y≤1; or        Li_(1+x+y)M_(x)Sc_(2−x)Q_(y)P_(3−y)O₁₂, with M=Al, Y, Ga or a        mixture of the three compounds and Q=Si and/or Se, 0≤x≤0.8 and        0≤y≤1; or Li_(1+x+y+z)M_(x)(Ga_(1−y)Sc_(y))_(2−x)Q_(z)P_(3−z)O₁₂        with 0≤x≤0.8; 0≤y≤1; 0≤z≤0.6 with M=Al or Y or a mixture of the        two compounds and Q=Si and/or Se; or Li_(1+x)N_(x)M_(2−x)O₁₂,        with 0≤x≤1 and N═Cr and/or V, M=Se, Sn, Zr, Hf, Se or Si, or a        mixture of these compounds;    -   lithiated borates, preferably chosen from:        Li₃(Sc_(2−x)M_(x))(BO₃)₃ with M=Al or Y and 0≤x≤1;        Li_(1+x)M_(x)(Sc)_(2−x)(BO₃)₃ with M=Al, Y, Ga or a mixture of        the three compounds and 0≤x≤0.8; 0≤y≤1;        Li_(1+x)M_(x)(Ga_(1−y)Sc_(y))_(2−X)(BO₃)₃ with 0≤x≤0.8; 0≤y≤1        and M=Al or Y; Li_(1+x)M_(x)(Ga)_(2−x)(BO₃)₃ with M=Al, Y or a        mixture of the two compounds and 0≤x≤0.8; 0≤y≤1; Li₃BO₃,        Li₃BO₃—Li₂SO₄, Li₃BO₃—Li₂SiO₄, Li₃BO₃—Li₂SiO₄—Li₂SO₄;    -   oxynitrides, preferably chosen from Li₃PO_(4−x)N_(2x/3),        Li₄SiO_(4−x)N_(2x/3), Li₄GeO_(4−x)N_(2x/3) with 0<x<4 or        Li₃BO_(3−x)N_(2x/3) with 0<x<3; the materials based on lithium,        phosphorus or boron oxynitrides (called LiPON and LIBON) may        also contain silicon, sulfur, zirconium, aluminum, or a        combination of aluminum, boron, sulfur and/or silicon, and boron        for lithium phosphorus;    -   lithiated oxides, preferably chosen from Li₇La₃Zr₂O₁₂ or        Li_(5+x)La₃(Zr_(x),A_(2−x))O₁₂ with A=Sc, Y, Al, Ga and 1.4≤x≤2        or Li_(0.35)La_(0.55)TiO₃; and    -   silicates, preferably chosen from Li₂Si₂O₅, Li₂SiO₃, Li₂Si₂O₆,        LiAlSiO₄, Li₄SiO₄, and LiAlSi₂O₆;

Preferably, when an electrolyte material layer is deposited only on thelayer obtained in step b), an electrolyte material layer chosen from thefollowing is deposited:

-   -   Li₃(Sc_(2−x)M_(x))(PO₄)₃ with M=Al or Y and 0≤x≤1; or;    -   Li_(1+x)M_(X)(Sc)_(2−x)(PO₄)₃ with M=Al, Y, Ga or a mixture of        two or three compounds and 0≤x≤0.8; 0≤y≤1.0; or;    -   Li_(1+x)M_(x)(Ga)_(2−x)(PO₄)₃ with M=Al, Y or a mixture of the        two compounds M and 0≤x≤0.8; 0≤y≤1.0; or;    -   Li_(1+x)M_(x)(Ga_(1−y)Sc₁)_(2−x)(PO₄)₃ with 0≤x≤0.8; 0≤y≤1.0 and        M=Al or Y; or a mixture of the two compounds; or    -   Li_(1+x)Al_(x)Ti_(2−x)(PO₄)₃ with 0≤x≤1; or    -   Li_(1+x)Al_(x)Ge_(2−x)(PO₄)₃ with 0≤x≤1; or    -   Li_(1+x+z)M_(x)(Ge_(1−y)Ti_(y))_(2−x)Si_(z)P_(3−z)O₁₂ with        0≤x≤0.8 and 0≤y≤1.0 and 0≤z≤0.6 and M=Al, Ga or Y or a mixture        of two or three compounds; or    -   lithiated oxides chosen from Li₇La₃Zr₂O₁₂ or        Li_(5+x)La₃(Zr_(x),A_(2−x))O₁₂ with A=Sc, Y, Al, Ga and 1.4≤x≤2,        Li_(0.35)La_(0.55)TiO₃ or Li_(0.5)La_(0.5)TiO₃;    -   lithiated borates, preferably chosen from:        Li₃(Sc_(2−x)M_(x))(BO₃)₃ with M=Al or Y and 0≤x≤1;        Li_(1+x)M_(x)(Sc)_(2−x)(BO₃)₃ with M=Al, Y, Ga or a mixture of        the three compounds and 0≤x≤0.8; 0≤y≤1;        Li_(1+x)M_(x)(Ga_(1−y)Sc_(y))_(2−x)(BO₃)₃ with 0≤x≤0.8; 0≤y≤1        and M=Al or Y; Li_(1+x)M_(x)(Ga)_(2−x)(BO₃)₃ with M=Al, Y or a        mixture of the two compounds and 0≤x≤0.8; 0≤y≤1; Li₃BO₃,        Li₃BO₃—Li₂SO₄, Li₃BO₃—Li₂SiO₄, Li₃BO₃—Li₂SiO₄—Li₂SO₄;    -   oxynitrides, preferably chosen from Li₃PO_(4−x)N_(2x/3),        Li₄SiO_(4−x)N_(2x/3), Li₄GeO_(4−x)N_(2x/3) with 0<x<4 or        Li₃BO_(3−x)N_(2x/3) with 0<x<3; the materials based on lithium,        phosphorus or boron oxynitrides (called LiPON and LIBON) may        also contain silicon, sulfur, zirconium, aluminum, or a        combination of aluminum, boron, sulfur and/or silicon, and boron        for lithium phosphorus;    -   silicates, preferably chosen from Li₂Si₂O₅, Li₂Si₂O₃, Li₂Si₂O₆,        LiAlSiO₄, Li₄SiO₄, LiAlSi₂O₆.

Advantageously, the solid electrolyte layer is produced byelectrophoretic deposition of electrolyte material nanoparticles, whichare electrically insulating. The layers obtained provide full coverage,without localized defects. The current deposition densities areconcentrated on the less insulating zones, in particular localized wherea defect may be present.

The absence of defects in the electrolyte layer prevents the appearanceof creeping short-circuits, excessive self-discharges, or even failureof the battery cell.

The performance of the batteries obtained by the process according tothe invention is partially due to the crystalline structure of theelectrolyte material(s). To obtain good battery performance, it isadvantageous to obtain an electrolyte of amorphous glass ornanocrystalline structures. Thus, to prevent growth of the grain size ofthe electrolyte materials after deposition, and to prevent reactionsfrom occurring at the interfaces, the assembly of the battery must notbe performed at a high temperature, i.e. at a temperature exceeding 300°C.

According to the invention, after the deposition of the electrolytematerial layer, a layer of a cross-linked polymer material comprisingionic groups is produced:

on the anode material layer coated with a solid electrolyte materiallayer and/or on the cathode material layer coated or not with a solidelectrolyte material layer;

or on the cathode material layer coated with a solid electrolytematerial layer and/or on the anode material layer coated or not with asolid electrolyte material layer.

Preferably, the cross-linked polymer material is chosen from any type ofpolymer containing the cationic groups described below. Morespecifically, the cross-linked polymer material is chosen frompolymethyl methacrylates, polyamines, polyimides or polysiloxanes.Preferably, the ionic groups of the polymer material are chosen from thefollowing cations: imidazolium, pyrazolium, tetrazolium, pyridinium,pyrrolidinium, such as n-propyl-n-methylpyrrolidinium (also calledPYR13) or n-butyl-n-methylpyrrolidinium (also called PYR14), ammonium,phosphonium or sulfonium; and/or from the following anions:bis(trifluoromethane)sulfonimide, bis(fluorosulfonyl)imide, orn-(nonafluorobutane-sulfonyl)-n-(trifluoromethanesulfonyl)-imide (of rawformula C₅F₁₂NO₄S₂, also called IM14-). The use of such anions makes itpossible to preserve good properties of resistance to exposure to airand moisture, thereby simplifying the industrial implementation andguaranteeing better performance in terms of battery lifetime. Inaddition, the layer of cross-linked polymer material comprising ionicgroups makes it possible to ensure the safety and lifetime of thebattery by protecting it from risks of short circuit and ignition ofsolvent. In fact, these polymer materials are all-solid and do notcontain any liquid electrolyte or electrolyte dissolved in a solvent.Moreover, these cross-linked polymer materials resist high temperatureswithout the risk of evaporation or ignition of an organic solvent.

In an embodiment of the process according to the invention, thecross-linked polymer material comprising ionic groups is depositeddirectly by dip-coating, spin-coating, roll coating, doctor blade,electrospraying or electrophoresis. For this, the polymer material isfirst dissolved in an appropriate solvent, the polymer materialdissolved on the anode, cathode and/or electrolyte layer(s) isdeposited, then the polymer material layer is dried before the solventis removed.

Advantageously, the deposition of the cross-linked polymer material isperformed by electrophoresis in order to limit the defects in the layerthat may cause short circuits in the final battery. The deposition byelectrophoresis makes it possible to obtain a dense and compact layer.In addition, the electrophoretic deposition makes it possible to reducethe risk of cracking of the layer after drying, unlike the layersproduced by inks or fluids, having low dry extracts and for which thedeposits contain large amounts of solvent, which, after drying, leads tothe appearance of cracks in the deposit, which is detrimental to theoperation of a battery.

In another embodiment of the process according to the invention, amonomer and/or an oligomer and/or a pre-polymer including one or morepolymerizable groups is deposited. Preferably, a pre-polymer includingone or more reactive groups is deposited, enabling the grafting of ionicgroups. The polymerization is performed thermally and/or photochemicallydirectly on the anode, cathode or electrolyte layer(s). Typically, thepolymerization is performed in the presence of a thermal initiator, forexample chosen from benzoyl peroxide, acetyl peroxide orazoisobutyronitrile, and/or a photochemical initiator, for examplechosen from benzoin, an acetophenone, such as2,2-dimethoxy-2-phenylacetophenone or 2,2-diethoxyacetophenone.

The deposition of a cross-linked polymer material comprising ionicgroups makes it possible to considerably increase the ionic conductivityof the electrolyte. In addition, these materials are relativelynon-flammable, resistant to high temperature, and have a negligiblevapor pressure. The cross-linked polymer layer comprising ionic groupsthus makes it possible to produce a thin-layer three-dimensional batterywithout using a heat treatment and/or extreme mechanical compressionduring the step of assembly of said battery.

In fact, the production of at least one layer of cross-linked polymermaterial comprising ionic groups makes it possible to assembleelectrodes at low temperature, i.e. a temperature not exceeding 300° C.,preferably 200° C. and even more preferably 150° C. Advantageously, anionic liquid, PYR 13, PYR 14 and/or a lithium salt may be dissolved insaid cross-linked polymers comprising ionic groups. The addition of anionic liquid, PYR 13, PYR 14 and/or a lithium salt is beneficial forelectrochemical performance, and this addition makes it possible toimprove conduction but also makes it possible to reduce the rigidity ofthe polymer film, which, without this addition, remains highlybreakable.

According to a particular embodiment of the process of the invention,the electrodes (anode and cathode) are “punched” according to a cuttingpattern in order to produce cuts with the dimensions of the battery tobe produced. The punching of the electrodes may be performed after stepc) of deposition of the electrolyte layer, or after step d) ofdeposition of the layer of cross-linked polymer material comprisingionic groups. These patterns include three cuts that are adjoined (forexample in a U shape), and which define the dimension of the battery. Asecond slot may be produced on the non-cut side in order to make itpossible to ensure that products necessary for encapsulation of thecomponent can pass. The anode and cathode electrodes are then stackedalternately in order to form a stack of a plurality of basic cells. Theanode and cathode cutting patterns are placed in a “head-to-tail”configuration.

In another particular embodiment of the process according to theinvention, the electrodes are cut before step c) of deposition of theelectrolyte layer(s), enabling the electrode edges to be covered by anelectrolyte film, thus protecting the electrodes from contact with theatmosphere, and enabling the lifetime of the battery to be improved. Inan alternative embodiment, the cuts are produced on the substratesbefore steps a) and b) of deposition of the anode and cathode layer,enabling the electrode edges to be covered by an electrolyte film. Thisparticular embodiment has the advantage of covering the electrode edgesbefore the layer of electrolyte material nanoparticles is deposited,thereby enabling an encapsulation film to be easily produced around theelectrodes, in particular when the electrolyte layer is comprised ofmoisture-stable materials. The covering of the lateral edges of theelectrodes also makes it possible to reduce the risks of short circuitin the cell.

Finally, an essential step of the process according to the inventionincludes a heat treatment and/or mechanical compression of the stackobtained above in order to obtain an all-solid thin-layer battery. Theheat treatment is performed at a temperature of between 50 and 300° C.,preferably 100 and 200° C. Advantageously, the temperature of the heattreatment does not exceed 200° C. Advantageously, the mechanicalcompression of the layers to be assembled is performed at a pressure ofbetween 10 and 100 MPa, and preferably between 20 and 50 MPa.

In a particular embodiment, it is advantageous, after the step ofstacking and before the addition of terminals, to encapsulate the stackby depositing a thin encapsulation layer in order to ensure theprotection of the battery cell from the atmosphere. The encapsulationlayer must be chemically stable, resist high temperatures and beimpermeable to the atmosphere in order to perform its function asbarrier layer. Preferably, the thin encapsulation layer consists of apolymer, a ceramic, a glass or a vitroceramic, capable of being, forexample, in oxide, nitride, phosphate, oxynitride or siloxane form. Evenmore preferably, this encapsulation layer is coated with an epoxy orsilicone resin.

The encapsulation layer may advantageously be deposited by chemicalvapor deposition (CVD), which makes it possible to provide coverage ofall the accessible stack surfaces. Thus, the encapsulation may beperformed directly on the stacks, the coating being capable ofpenetrating all of the available cavities. Advantageously, a secondencapsulation layer may be deposited on the first encapsulation layer inorder to increase the protection of the battery cells from the externalenvironment. Typically, the deposition of said second layer may beperformed by silicone impregnation. The choice of such a material isbased on the fact that it is resistant to high temperatures and thebattery may thus be easily assembled by welding on electronic cardswithout the appearance of glass transitions.

Advantageously, the encapsulation of the battery is performed on four ofthe six faces of the stack. The encapsulation layers surround theperiphery of the stack, with the remainder of the protection from theatmosphere being ensured by the layers obtained by the terminals.

Preferably, the cathode and anode connections are laterally offset,enabling the encapsulation layer to operate as a dielectric layer inorder to prevent the presence of a short circuit at these ends.

Once the stack has been produced, and after the step of encapsulation ofthe stack if it is performed, terminals (electrical contacts) are addedwhere the cathode or anode current collectors, respectively, are exposed(not coated with encapsulation layers). These contact zones may be onopposite sides of the stack in order to collect the current, but also onadjacent sides.

To produce the terminals, the stack, optionally coated, is cut accordingto cutting planes making it possible to obtain unitary batterycomponents, with exposure on each of the cutting planes of connections(+) and (−) of the battery. The connections may then be metallized bymeans of plasma deposition techniques known to a person skilled in theart and/or by immersion in a conductive epoxy resin (filled with silver)and/or a molten tin bath. The terminals make it possible to establishalternately positive and negative electrical connections on each of theends. These terminals make it possible to produce the electricalconnections in parallel between the different battery elements. Forthis, only the (+) connections emerge at one end, and the (−)connections are available at the other ends.

As this battery is all-solid, and uses a lithium insertion material asthe anode material, the risks of formation of metallic lithium dendritesduring the recharging steps are zero and the capacity for insertion ofthe lithium anode becomes limited.

In addition, to ensure good cycling performance of the battery accordingto the invention, the battery architecture for which the surfacecapacity of the cathodes is greater than or equal to the surfacecapacity of the anodes is preferred.

As the layers forming the battery are all-solid, the risk of formationof lithium dendrites no longer exists when the anode is fully charged.Thus, such a battery architecture avoids the creation of an excess ofbattery cells.

In addition, the production of such a battery with cathode surfacecapacities greater than or equal to those of the anodes makes itpossible to increase performance in terms of lifetime, expressed as anumber of cycles. In fact, as the electrodes are dense and all-solid,the risk of loss of electrical contact between the particles is zero.Moreover, there is no longer a risk of metallic lithium deposit in theelectrolyte or in the porosities of the electrodes, and finally there isno risk of deterioration of the crystalline structure of the cathodematerial.

EXAMPLE

A suspension of the anode material was obtained by grinding thendispersion of Li₄Ti₅O₁₂ in 10 g/l of absolute ethanol with several ppmof citric acid.

A suspension of cathode material was obtained by grinding/dispersion ofLiMn₂O₄ in 25 g/l of absolute ethanol. The cathode suspension was thendiluted in acetone to a concentration of 5 g/l.

The suspension of ceramic electrolyte material was obtained bygrinding/dispersion of a powder of Li₃Al_(0.4)Sc_(1.6)(PO₄)₃ in 5 g/l ofabsolute ethanol.

For all of these suspensions, the grindings were performed so as toobtain stable suspensions with particle sizes smaller than 100 nm.

The negative electrodes were prepared by electrophoretic deposition ofthe Li₄Ti₅O₁₂ nanoparticles contained in the suspension previouslyprepared. The thin film of Li₄Ti₅O₁₂ (around 1 micron) was deposited onthe two faces of the substrate. These negative electrodes were thenheat-treated at 600° C.

The positive electrodes were prepared in the same way, byelectrophoretic deposition from the LiMn₂O₄ suspension. The thin film ofLiMn₂O₄ (around 1 μm) was deposited on the two faces of the substrate.The positive electrodes were then treated at 600° C.

After the heat treatment, the negative electrodes and the positiveelectrodes were covered with a ceramic electrolyte layerLi₃Al_(0.4)Sc_(1.6)(PO₄)₃ by electrophoretic deposition. The LASPthickness was measured and is around 500 nm on each electrode. Theseelectrolyte films were then dried by heat treatment.

The polymer formulation used to produce the assembly of the battery cellconsisted of polyethylene glycol monomomethylacrylate with an ionicliquid 1-butyl-3-methylimidazolium tetrafluoroborate [BMIm][BF4] (in amass proportion of around 3:7) and a lithium salt (lithium (lithiumbis(trifluoromethansulfonyl)imide or LiTFSI). A photoinitiator (around1% by mass), in this case 2,2′-dimethoxy-2-phenylacetophenone (Irgacure™651, Ciba-Geigy) was added. The cross-linking was obtained byirradiation at 366 nm for 10 minutes at ambient temperature, in an argonatmosphere.

The electrodes coated with a solid electrolyte film were then coatedwith a fine layer of ionic liquid polymers by dip-coating (dippingfollowed by drying). The stack of anodes and cathodes was then producedin order to obtain a multilayer stack. The assembly was kept underpressure for 15 minutes at 100° C. in order to produce the assembly.

The battery thus obtained was cycled between 2 and 2.7 V, and FIGS. 1and 2 show the charge and discharge curves obtained.

What is claimed is:
 1. A process for producing an all-solid, thin-layerbattery, the process comprising: a) depositing at least one anodematerial layer on an anode current collecting conductive substrate toform a solid anode; b) depositing at least one cathode material layer ona cathode current collecting conductive substrate to form a solidcathode; c) depositing at least one solid electrolyte material layer onat least one of the solid anode and the solid cathode to forming a solidelectrolyte layer; d) depositing, after forming the solid electrolytelayer, a cross-linked polymer material comprising ionic groups on: theat least one anode material layer coated with the at least one solidelectrolyte material layer and/or the at least one cathode materiallayer uncoated or coated with the at least one solid electrolytematerial layer; or the at least one cathode material layer coated withthe at least one solid electrolyte material layer and/or on the anodematerial layer uncoated or coated with the at least one solidelectrolyte material layer; e) stacking the solid anode obtained in a),c) or d) in series with the solid cathode obtained in b), c) or d); andf) performing a heat treatment and/or a mechanical compression of thestack obtained in e).
 2. A process for producing an all-solid,thin-layer battery, the process comprising: a) forming a solid anode bydepositing at least one anode material layer on a first conductivesubstrate formed by a metal sheet, or a metal strip, or a metallizedinsulating sheet, or a metallized insulating strip, or a metallizedinsulating film, said first conductive substrate, or conductive elementsthereof, configured to serve as an anode current collector; b) forming asolid cathode by depositing at least one cathode material layer on asecond conductive substrate formed by a metal sheet, or a metal strip,or a metallized insulating sheet, or a metallized insulating strip, or ametallized insulating film, said second conductive substrate, orconductive elements thereof, configured to serve as a cathode currentcollector; c) forming a solid electrolyte layer by depositing on atleast one of the solid anode and the solid cathode, at least one solidelectrolyte material layer; d) depositing, after forming the solidelectrolyte layer, a cross-linked polymer material comprising ionicgroups having a thickness of less than 2 μm, on: the at least one anodematerial layer coated with the solid electrolyte material layer and/orthe at least one cathode material layer uncoated or coated with thesolid electrolyte material layer; or the at least one cathode materiallayer coated with the solid electrolyte material layer and/or on theanode material layer uncoated or coated with the solid electrolytematerial layer; e) stacking the at least one anode material layerobtained in a), c) or d) face to face in series with the at least onecathode material layer obtained in b), c) or d) such that the stackincludes at least one solid electrolyte material layer obtained in c)and at least one cross-linked polymer material layer obtained in d); andf) performing a heat treatment and/or a mechanical compression of thestack obtained in e) to obtain the all-solid, thin-layer battery.
 3. Theprocess of claim 2, wherein the at least one cross-linked polymermaterial is chosen from polymethyl methacrylates, polyamines,polyimides, or polysiloxanes.
 4. The process of claim 2, wherein theionic groups of the polymer material are chosen from the followingcations: imidazolium, pyrazolium, tetrazolium, pyridinium,pyrrolidinium, ammonium, phosphonium or sulfonium; and/or from thefollowing anions: bis(trifluoromethane)sulfonimide,bis(fluorosulfonyl)imide, orn-(nonafluorobutane-sulfonyl)-n-(trifluoromethanesulfonyl)-imide.
 5. Theprocess of claim 2, wherein the at least one cross-linked polymermaterial is obtained by: polymerization of a mixture of monomers, and/oroligomers, and/or pre-polymers including one or more thermally orphotochemically polymerizable groups, said mixture of monomers and/oroligomers and/or pre-polymers including one or more reactive groupsenabling said ionic groups to be grafted.
 6. The process of claim 5,wherein the thermal and/or photochemical polymerization is performeddirectly on the solid anode, the solid cathode, and/or the solidelectrolyte layer.
 7. The process of claim 2, wherein the at least oneanode material layer, and/or the at least one cathode material layerinclude graphite, and/or nanoparticles of lithium ion conductivematerials, or cross-linked solid polymer materials comprising ionicgroups.
 8. The process of claim 2, wherein: producing the solid anodecomprises depositing nanoparticles of at least one anode material usingelectrophoresis; and/or producing the solid cathode comprises depositingnanoparticles of at least one cathode material using electrophoresis;and/or producing the solid electrolyte layer comprises depositingnanoparticles of at least one electrolyte material usingelectrophoresis.
 9. The process of claim 8, wherein the nanoparticles ofthe at least one electrolyte material have a size less than 30 nm. 10.The process of claim 2, wherein the at least one anode material layer isproduced from a material chosen from: (i) tin oxynitrides; (ii)lithiated iron phosphate; (iii) mixed silicon and tin oxynitrides(formed as SiSn_(0.87)O₁₂N_(1.72); as well as oxynitrides-carbidesformed as Si_(a)Sn_(b)C_(c)O_(y)N_(z), with a>0, b>0, a+b≤2, 0<c<10,0<y<24, 0<z<17; Si_(a)Sn_(b)C_(c)O_(y)N_(z)X_(n) with X_(n) comprisingat least one of the elements among F, Cl, Br, I, S, Se, Te, P, As, Sb,Bi, Ge, Pb and a>0, b>0, a+b>0, a+b≤2, 0<c<10, 0<y<24 and 0<z<17; andSi_(a)Sn_(b)O_(y)N_(z)X_(n) with X_(n) comprising at least one of theelements among F, Cl, Br, I, S, Se, Te, P, As, Sb, Bi, Ge, Pb and a>0,b>0, a+b≤2, 0<y≤4 and 0<z≤3; (iv) nitrides of type Si_(x)N_(y) (with x=3and y=4), Sn_(x)N_(y) (with x=3 and y=4), Zn_(x)N_(y) (with x=3 andy=4), and Li_(3−x)M_(x)N (with M=Co, Ni, Cu); (v) oxides SnO₂,Li₄Ti₅O₁₂, SnB_(0.6)P_(0.4)O_(2.9) and TiO₂.
 11. The process of claim 2,wherein the at least cathode material layer is produced from materialchosen from: oxides LiMn₂O₄, LiCoO₂, LiNiO₂, LiMn_(1.5)Ni_(0.5)O₄,LiMn_(1.5)Ni_(0.5−x)X_(x)O₄ (in which X is selected from Al, Fe, Cr, Co,Rh, Nd, and other rare earth elements, and in which 0<x<0.1), andLiFeO₂, LiMn_(1/3)Ni_(1/3)CO_(1/3)O₄; (ii) phosphates LiFePO₄, LiMnPO₄,LiCoPO₄, LiNiPO₄, Li₃V₂(PO₄)₃, phosphates of formula LiMM′PO₄, with Mand M′ (M≠M′) selected from Fe, Mn, Ni, Co, V; (iii) all lithiated formsof the following chalcogenides: V₂O₅, V₃O₈, TiS₂, titanium oxysulfides(TiO_(y)S_(z)), tungsten oxysulfides (WO_(y)S_(z)), CuS, and CuS₂. 12.The process of claim 2, wherein the electrolyte material layer isproduced from electrolyte material chosen from: garnets of formulaLi_(d)A1_(x)A2_(y)(TO₄)_(z), wherein A1 represents a cation of oxidationnumber +II, A2 represents a cation of oxidation number +III, and TO₄represents an anion in which T is an atom of oxidation number +IV,located at the center of a tetrahedron formed by oxygen atoms, and inwhich TO₄ represents a silicate or zirconate anion, in which all or someof the elements T with an oxidation number +IV may be replaced by atomswith an oxidation number +III or +V, wherein d is between 4 and 8, x isbetween 2.8 and 3.2, y is between 1.9 and 2.1, and z is between 2.9 and3.1; garnets chosen from: Li₇La₃Zr₂O₁₂; Li₆La₂BaTa₂O₁₂;Li_(5.5)La₃Nb_(1.75)In_(0.25)O₁₂, Li₅La₃M₂O₁₂, with M=Nb or Ta or amixture of the two compounds, Li_(7−x)Ba_(x)La_(3−x)M₂O₁₂ with 0≤x≤1 andM=Nb or Ta or a mixture of the two compounds, orLi_(7−x)La₃Zr_(2−x)M_(x)O₁₂ with 0≤x≤2 and M=Al, Ga or Ta or a mixtureof two or three of said compounds; lithiated phosphates chosen from:Li₃PO₄; Li₃(Sc_(2−x)M_(x))(PO₄)₃ with M=Al or Y and 0≤x≤1;Li_(1+x)M_(x)(Sc)_(2−x)(PO₄)₃ with M=Al, Y, Ga or a mixture of the threecompounds and 0≤x<0.8; Li_(1+x)M_(x)(Ga_(1−y)Sc_(y))_(2−x)(PO₄)₃ with0≤x≤0.8; 0≤y≤1 and M=Al or Y or a mixture thereof;Li_(1+x)M_(x)(Ga)_(2−x)(PO₄)₃ with M=Al, Y or a mixture thereof and0≤x≤0.8; Li_(1+x)Al_(x)Ti_(2−x)(PO₄)₃ with 0≤x≤1, orLi_(1+x)Al_(x)Ge_(2−x)(PO₄)₃ with 0≤x≤1; orLi_(1+x+z)M_(x)(Ge_(1−y)Ti_(y))_(2−x)Si_(z)P_(3-z)O₁₂ with 0≤x≤0.8 and0≤y≤1.0 and 0≤z≤0.6 and M=Al, Ga or Y or a mixture of two or threecompounds thereof; Li_(3+y)(Sc_(2−x)M_(x))Q_(y)P_(3-y)O₁₂, with M=Aland/or Y and Q=Si and/or Se, 0≤x≤0.8 and 0≤y≤1; orLi_(1+x+y)M_(x)Sc_(2−x)Q_(y)P_(3-y)O₁₂, with M=Al, Y, Ga or a mixturethereof and Q=Si and/or Se, 0≤x≤0.8 and 0≤y≤1; orLi_(1+x+y+z)M_(x)(Ga_(1−y)Sc_(y))_(2−x)Q_(z)P_(3−z)O₁₂ with 0≤x≤0.8;0≤y≤1; 0≤z≤0.6 with M=Al or Y or a mixture thereof and Q=Si and/or Se;or Li_(1+x)N_(x)M_(2−x)P₃O₁₂, with 0≤x≤1 and N═Cr and/or V, M=Se, Sn,Zr, Hf, Se or Si, or mixtures thereof; lithiated borates chosen from:Li₃(Sc_(2−x)M_(x))(BO₃)₃ with M=Al or Y and 0≤x≤1;Li_(1+x)M_(x)(Sc)_(2−x)(BO₃)₃ with M=Al, Y, Ga or a mixture thereof and0≤x≤0.8; 0≤y≤1; Li_(1+x)M_(x)(Ga_(1-y)Sc_(y))_(2−x)(BO₃)₃ with 0≤x≤0.8;0≤y≤1 and M=Al or Y; Li_(1+x)M_(x)(Ga)_(2−x)(BO₃)₃ with M=Al, Y or amixture thereof and 0≤x≤0.8; 0≤y≤1; Li₃BO₃, Li₃BO₃—Li₂SO₄,Li₃BO₃—Li₂SiO₄, Li₃BO₃—Li₂SiO₄—Li₂SO₄; oxynitrides chosen fromLi₃PO_(4−x)N_(2x/3), Li₄SiO_(4−x)N_(2x/3), Li₄GeO_(4−x)N_(2x/3) with0<x<4 or Li₃BO_(3−x)N_(2x/3) with 0<x<3, materials based on lithium,phosphorus or boron oxynitrides that may also contain silicon, sulfur,zirconium, aluminum, or a combination of aluminum, boron, sulfur and/orsilicon, and boron for lithium phosphorus; lithiated oxides chosen fromLi₇La₃Zr₂O₁₂ or Li_(5+x)La₃(Zr_(x),A_(2−x))O₁₂ with A=Sc, Y, Al, Ga and1.4≤x≤2 or Li_(0.35)La_(0.55)TiO₃; silicates chosen from Li₂Si₂O₅,Li₂SiO₃, Li₂Si₂O₆, LiAlSiO₄, Li₄SiO₄, and LiAlSi₂O₆.
 13. The process ofclaim 2, further comprising, after f): g) encapsulating the all-solid,thin-film battery by depositing at least one layer of a ceramicmaterial, a vitreous material, or a vitroceramic material.
 14. Theprocess of claim 2, further comprising producing an anode terminal and acathode terminal by deposition of a tin layer.